Improved cadmium halophosphate phosphors



Maw}! 15, 1954 R. w. WOLLENTIN ET AL 2,672,451

IMPROVED CADMIUM HALOPHOSPHATE PHOSPHORS Filed Feb. 2, 1951 l INVENTORS R. w. WOLLENT'IN RUDOLPH NAeY.

ATTORNE Patented Mar. 16, 1954 BHOSPH ORS Robert W. Wollentin, Bloomfield, and-Rudolph Nagy, Upper'Montclair, N .-J assignors to W est.- inghouse :Elec'trib Corporation, Ea's't Pitt'sburgh, Pm, a' corporation of Pennsylvania A'pplication'February 2, 19.51, deriallslo.2091090 13*Claims. 1 This invention relates'to phosphors, methods of making, and, more particularly, to an imloved phosphor o'fthe cadmiumhalophosphme Th .principal object of' ou'r invention, "generally considered, is to. produce an efii'cierit phosphor comprising icadmium phosphate activated by manganese, and halidessupphedxby material of the group consisting of a zinc halide,,magnesiu'm h'alide, "strcntium rhalide, and a compound-of b'ar-iumssucha's the'halide.

nnother-iob'ject of cur -invention is to increase ztlreiefiiciency and stability or" emission of cadmium:halbphosphate:activatedby manganese, by the inclusion of zine-halide, thereby causing a slight shift; ithe maximum of the emission spectrum fromiasnormahpealsaxtabout.5900.A.'.U.,

toward the -red,,-andbroadening said spectrum on both the long and-rshortzwave length sides.

A further object efqour zinvention isite obtain the optimum efliciency in a manganese-activated cadmium halophosphatesephosphor by employing, for each 3 moles of cadmium phosphate, about UL G moIe of magnesium chloride and .4 mole of Zinc chloride; with :2 'moie-of manganese, also incorporating --from @225 to 0 25 mole excess of #phosphate over thatrequired -to-for'm 1 the or-thophosphate.

A still further object of our invention is to use:strontiuin' ehloride m a manganese-activated cadmium chlorophospliate phosphor' -as a source of :halide, and drum 8:25 to 10:5 emote excesscf phosphate, "thereby dmproviiig the luminescent output.

Another obj eet of' our 1 -inventioniis to improve on the emciency ef ima aneseeactivated =-.ca;d-

m1um halophosphates by the addition of barium chloridethereto.

A further object of our invention is to apply such luminescent materials,iasabove defined, to envelopes for fluorescent lamps as coatings of (optimum thickness, and lehr them at optimum "temperatures.

A "still further "object "of our "invention is to blend phosphors, such as 1 thos -altborve idfine d, with supplementary --luminescent -ma-ter-ials 'i-n order-to obtain white lightpha dsird qdflity.

An additional object of our. invention is touse tl'ie te minat as me sour'ce'ereaummm m cadmium em-orophosphates, r0 therebyobtainsome advar'itage;as cenrpareawitirtre use tame-exists.

entias th'e descriptionproceds.

rReferring to rtheadrawing-the sclez figure .is ia i 'trili-nearizcliart ashc'wing cthe fieffeotst i utput cation variatiom the halogen-s pplyin sp rtion of 30d; (P04) 2.2 (Sr,Zn,Ba) C12 0.2Mn, when the firing temperature is 750 C.

The luminescent materials known as the-cadmi-um' chloropho'sphates activated -'by manganese have been used in such devices as low pressure mercury discharge lamps and cathode ray tubes to produceyellowish-pink lig'htwith an emission peak and-about 5900 U. In the syntheses of these materials, the chloride; component has been supplied by "either magnesium chloride or cadmium chloride, the 'former producing the more efiicient'phosphors.

'-We have foundthat the efliciencyof emission and the stability of the material under excita-' tion can be improved by the inclusion-of zinc chloride which, in conjunction with magnesium chloride, causes a slight-shift of the peak of emission toward the red,amaximum of 50 A. U. It also broadens-the emission spectrum .onboth the long and shortwavelength sides. The overall effect is an increase in total lumensrper .watt output of a fluorescent lamp incorporating such an improved phosphor.

The degree of' improvement is dependentcupon the amount of zinc-=chloride incorporated. .JAsa convenientmethod of representing the proportions of constituents, the following formula s. can

be applied: =3Cd3 (P04 )2; (Mg ,Zn) C12 :rtMn, ,Wherein the atotal :amount of :halide may vary from 0.8 i to 1 .5 moles; andl the mol'e-ratioaof :zinc chloride :to imagnesium :chlori-de does not exceed 2 to .3. 5A ratio' t'ofproduce@optimum :efiiciencyis 3 moles Cd3(PO4)2 to 0.6 mole of MgCIzand -HOA mole ZnCl2, with 0;2.mole MnClz. 'sAs ordinary magnesium chloride isashighly. deliquescentmavterial, and is therefore difiicult to handle, .wey se he :same mole .ratio of aifused mag- I nesiumzchloride, i or' arfused magnesium :oxychlo- :rid'e product :obtainable andxwhich corresponds essentially to thel'formulation .MgzOClz, which is practically 'non-deliquescent ;-and yields about the same resultsas the hydratediMgClz.

:The amount of manganese inttth i-formula can vary from 0.01 *to :21) :moles per c3.'0 ZIIIOIESJIOf side'red tube-optimum. :Man'ganese may be introduced as the phosphate, the carbonate, :the sulphate, the chloride or aszgan oxide. The chloride gives better resultsthanthe phosphate and the carbonate gives the lowest output.

It is highly advisable to incorporate at least 0.5 mole excess of phosphate over that required to form cadmium orthophosphate to produce a satisfactory white material. Lesser amounts lead to i. physic al discoloration and jQlCiMJEr :amounts cause a slight shift: ofizemission 1 toward the ,red,

accompanied by. andecrease in duorescentzbright- I SS- l The phosphor may be prepared by dry mixing,

wet mixing, or precipitation methods. For example, a good dry mix method producing highly fluorescent material is to mix 231.1 grams of cadmium oxide (060), 198 grams of di-ammonium acid phosphate ((NH4)2HPO4), 10.9 grams of zinc chloride (ZnClz), 24.4 grams of hydrated magnesium chloride (MgC12.6HzO), and 7.92 grams of hydrated manganese chloride (MnClzAl-IzO), in a blending apparatus until the preliminary dry state reaction is complete, followed by a grinding operation, such as hammer milling or ball milling for one or more hours, and finally firing in a covered tray to prevent excessive volatilization for 1.5 to 4 hours at a temperature of 700 to 980 C., with shorter time for the higher temperature. Th resultant material is soft, white, finely divided, and ready for use.

A wet mix method yielding satisfactory re- .sults is to use the same proportions as above,

but add sufficient distilled water or acetone to make a thick paste and wet mill for at least two hours, preferably four hours, evaporate to dryness, crush and grind either by ball mill or hammer mill, and fire as in the dry method.

A precipitation method may be to dissolve 555.3 grams of hydrated cadmium nitrate Cd(NO3)2.4H2O; 24.4 grams of hydrated magnesium chloride MgCl26H2O; 10.9 grams of zinc chloride; and 7.92 grams of hydrated manganese chloride MnClz4HzO; in 1.5 liters of boiling distilled water. Add slowly, with stirring, 198.5 grams of di-ammonium acid phosphate (NH4)2HPO4, dissolved in 300 ml. of distilled ,water at 70 C. Evaporate to dryness, crush to a fine powder and fire as in the dry mix method.

In any of the above methods, any cadmium salt, such as cadmium carbonate (Cd(CO3)), cadmium oxalate (021C204), etc., which will combine upon heating with di-ammonium acid phosphate to produce cadmium phosphate, may be substituted for cadmium oxide (CdO) or hydrated cadmium nitrate (Cd(NO3)24I-I2O). The :improved phosphor, when incorporated with a device, such as a low pressure mercury vapor discharge lamp, would produce light at a greater efiiciency and maintain a higher output throughout lamp life than a similar material not including zinc chloride in accordance with our invention.

Summarizing the results of including zinc -chloride in a manganese activated cadmium phosphate phosphor, we presence of the zinc serves would say that the to spread the emission spectrum slightly, more predominately on the short wave-length side, causing the light to become more yellowish. In 40 watt fluorescent lamps, the improved phosphor gave 59.1 lumens per watt at zero, and 55.3 lumens per watt at 100 hours, compared with 48.7 at zero and 44.8 at 100 hours for the unimproved phosphor.

The following examples indicate how the proportions of ingredients in the mixture may be chosen.

Example 1 The raw materials may consist of:

Cadmium oxide (CdO) Di-ammonium acid phosphate ((NH4)2HPO4) 7 Hydrated magnesium chloride (MgC126HsO). 0. Zinc Chloride (ZnOlz) Hydrated manganese chloride (MnOl2.4Hz0)...

The chemicals employed are desirably of phosphor grade and mixed in a blender for about an hour. Fused magnesium chloride or magnesium oxychloride, in the same mole proportion, may be substituted for the hydrated magnesium chloride. At this stage a reaction sets in, as evidenced by the liberation of heat and ammonia fumes. The mixing is best completed by hammer milling, or ball milling for from 1 to 3 hours. Finally, the material is fired in covered silica dishes for l to 4 hours at temperatures from 700 to980 0., preferably for one hour at about 800 C. for batches of the size above indicated. After reaction, the phosphor will have approximately the following mole composition.

3Cd3 (P04) 2.0.60MgC12 .0 .40ZI1C1202MI1C12 .0 .75P2O5 Example 2 Moles Cadmium carbonate (CdCO3) 9.0 Di-ammonium acid phosphate 7.5 Hydrated magnesium chloride .6 Zinc chloride 0.40 Manganese carbonate (MnCOa) 0.2 Ammonium chloride (NH4C1) 0.4

The amount of manganese can be varied from .01 to 2.0 moles per 3.0 moles of cadmium phosphate, 0.2 mole being considered optimum. When the manganese is used as a carbonate, ammonium chloride (or its equivalent) must be added to keep the halide content the same. The cadmium component may be the oxide, carbonate, or any other such compound which upon heating is converted to the oxide. The parts by weight are obtainable by multiplying the number of moles by the molecular weight.

Example 3 Moles Cadmium oxide 9.0 Di-ammonium acid phosphate 7.5 Zinc chloride 1.0 Hydrated manganese chloride 0.2

By replacing all of the magnesium chloride by an equal mole proportion of zinc chloride, a phosphor is obtained that has a slightly greater emission of both the yellow and red proportions of the spectrum. This gives a broader emission band. The finished phosphor will have a mole composition indicated by the following formula:

30d: (P04) 2.ZnC12.0.20MnCl2.0 .75P2O5 Example 4 (wet method) Moles Cadmium oxide 9.0 Phosphoric acid (H3PO4) 7.5 Hydrated magnesium chloride 0.6 Zinc chloride 0.4 Hydrated manganese chloride 0.2

When the phosphor is made by the wet method, the cadmium oxide is suspended in water with a mechanical stirrer and well mixed with the chlorides. Phosphoric acid is then added, possibly as a liquid of specific gravity 1.17, containing 87.1% of the constituent, and the whole evaporated to dryness at about 130 C. The product is ground in a mortar, and heated as in Exam- Pic #1.

aeram 5 Easimzzle rasses (o 'partsv by wt.) Hydrated cadmium nitrate- (Cd(NG3)'24I-I 20)L 5553 Di-ammonium-acid phosphate 198.5- Hydrated magnesium:chloride 24 .4 Zine chloride 1 10.9 Hydrated manganese chloride V592 The cadmium nitrate is diSSOIVQQQEiQ-Pli&a1it1 of boiling Water and. slowly added to the ammonium phosphate dissolved in one liter of boili water- The p c p tate is ashed br'deean tation, resuspended in 2, liters; of wateze contam ing- 39.6 grams of di-ammoniumi-aoidxnho hate. (NH4) 2HPO4. The manganese,- magnesium; and zinc halides are dissolved in 200 ml. of water and mixed with the cadmium phosphate; 'Ihesuspension is evaporated to dryness. and fired as Example #1.

We have found that strontium chlbridemay be used successfully as the source of halide and and allows a range of emission colors from 5900 A. U. to 6080 A. U.

In the preparation of our phosphors, we form a solid solution of tertiary cadmium phosphate, strontium chloride and manganese. A rangeof: strontium chloride concentration of 0.01- mole-of 5,;0 moles per 3. moles of tertiary phosphate is allowable; Manganese may be present-within the range of 0.001. moleto- 2.0- moles per 3 -moles of tertiary cadmium. phosphate.

The: optimum; amounts of strontium chloride and manganese for.- producing maximum output are 2.0.and.0.2'moles, respectively per-30 moles A; U. No advantageis known to be gainedby exceeding 50 moles of strontium chloride and, 2.0 moles ofmanganese, since-higher amounts reduce the output of the'resultant phosphors to, Ice-.- low'usable values.

In themanufacture; of these: materials; cadmium is preferablysupplied;by'the oxide .or care bonate, although; any compound of." cadmium that will react with a source of phosphateis allowable. The phosphateis-preferably supplied asdi-ammonium acid phosphate, although other sources such as mono-ammoniumacidv phosphate phosphorous pentoxide, P205, or phosphoric cid are, acceptable. Manganese is supplied prejerably as the chloride, although other compounds such as the oxide, sulfate, nitrate, carbonate and phosphate have been used with equal success. Anlexcess of? 0.251.to0:5 mole 0f phosphate per- 310' moles: of cadmium. is. necessary for highest eifi-- ciency-in allof these strontium-containing phosphors.

Thefollowing examples are-given'to illustrate means for applying the fundamentalsof-ourinventionto actual practice.

'Iihm raw materials: are; intimate y mixed? by grindingiin- .912 ballmill or by a; preliminary: blends in f operation; followed by: hammer milling; and fired in apcovered container for .1: temhourstat 950'-Q. to,:600?"C: respectively; mconven-ientiheat treatment; 12 /2; hours: attdooi" C. in a; covered silica; tray, The. resultant phosphor: has: 1,40% utput; compared to; unmodified:- GdziBQi) mm), and; an 1 emission; pealr: at; 5900 A 3U.

Example? wr- .2- ?s': r?! n'rR-n'rr r Mono,.-ammonium, acid phosphetew-sr a. .Stnontium... c bonatesrooo; a. a, o Hydrated cadmium, chloride, (QdClaZl/ v Manganese chloride This example is given" to" illustrate a second method of obtaining the same phosphor as in Example -6 Example 8 The same procedure andproportions are'used as in Example 6 except thestrontiumphlorideais increased to moles The resultant: n io ehor has an emission peak at 5930A U. and-appears, more pink under xcitation the nhosnhoriot Examplefii E-zmmplai? he same roc dure-ahaproportions-i amu ed asin Examp e .8 xoeptthatth manganese shiaride is increased to 0.50, mola, The; resultant phosphor has an emissionpealafitfiQ-A..U- and ppears more p nk than he phoseho in Ex: ample 8.

Example 11 0,-

The same procedure-and proportion areused as in Example .8; except thatithe man anese 1. ill: creased to 1.0 mole. Theresultantphosphonhas n m s n p k-lat .6080 A. L andao ears more. pink than. all the phosphors. in .EKamRIes, 6, 7, 8o.and.9..

Emomnlcrlli Example 1.12.

The s e pr p ns anofp ooedo e are used. as in Example 11', except that. the strontium chloride is increased to .510? moles. The resultantphosphor has an emission pealg at'6920 A, U:

Bhospho s, uc as b e d sclos d. we emeestured for plaque brightnessand made into A0 watt fluorescent lamps; The: output in lumens per watt, andcolor at zero and1'00ho rs, werealso obtained. Table I presents a summaryofjthese data. A. control hal'ophosphate was run simultaneou y a u s or zi e berstllium i io tewete addedjfor comparison. In a comparison of plaque brightnesses, the; cadmium phosphates were;.outstanding; The preparation of cadmium "halophosphate withmagnesium and/or-"zincr-prod-uoes about 16 greater output than zinc beryllium"silijeate and about 12% greater output: than the: standard -3500 whitecalcium-halophosphate.

T ph ph r e nt' ininat o m les o 'i ro -ti: um= chloride and ,2mo'le ofima n se an 'lu'men' values equal 'to' zinc beryllium silicate at zero hours, with slightlybetter maintenance.

Color values for these lamps are also given in the last column of Table I. These values placed the color temperature in the vicinity of 2040 to 2250 Kelvin. The phosphor containing one mole of manganese and 2 moles of strontium and the magnesium-zinc phosphor fall on the same isotemperature line. However, the former is 20 M. P. C. D. below the black body line while the 8 be supplied by the'diba's'lc or monobasic ammonium salt, or in the event of a wet or precipitation method, it may be supplied as orthophcsphoric acid. In any event, a 0.5 mole excess of phosphate per 3.0 moles of cadmium has been found to improve the output.

' The following examples are oifered to further demonstrate some compcsitions and methods that may be used in applying our invention to actual practice.

latter is only 2 M. PIC. D. below. Example 13 1 The phosphor containing 2.0 moles of .stron- Moles tium chloride and .0.2 mole of manganese is +2 Cadmium oxide 9.00 M. P. C. D. at 2174?. K. The remaining phosphor Di-ammonium acid phosphate 7 .50 containing 4 moles of strontium hada color 15 Barium chloride (Bach) ,2.00 temperature of 2250" K. +4 M. P. C. D. Hydrated manganese chloride 0.20

' I TABLE I Lumens Per 100 Hrs, Plaque W Percent Color Bright 1 Main.

0H1. 100Hrs. z y

cosmonauts ra es-0.44 znollzoalun 93. 3 e3. 2 s1. 4 s9. 5 520 412 3Cd3(PO4)2-2SrCl2:0.2Mn s9. 3 s5. 1 so. 5 92. a 510 no 3Od3(PO4)z-2SrClg:lMn 75.8 43. 9 a9. 7 90. a 7 292 (70d, 28:) (PO4)2-2SrClg:0.2Mn s4. 4 54 32. s 57. 0 502 420 3Ca3(P04)2-lCaFOl:Sb:Mn 83.0 72.7 ass 91.8 406 391 zneesiorml so. 0 66. 0 5s. 0 as. o 500 41s The a: and y of Table I are two of the three standard trichromatic coefiicients, :c, y. 2, set forth by the International Commission in Illumination. 1

They denote the ratio of colors weighted by concise distribution curves accepted as standard and covering the entire visible spectrum. For further clarification see: Jour. Opt. Soc. Am., 23,

manganese are caused to enter into solid solution by appropriate heat treatment. .Barium chloride may be added in proportions ranging from 0.01 to 6.0 moles per three moles of tertiary cadmium phosphate. An optimum amount of 2.0 moles of barium per 3.0 moles of tertiary cadmium phosphate has" been found to produce a maximum improvement of 45 per cent. The manganese may be varied from 0.01 to 2.0 moles per 3.0 moles of cadmium phosphate. However, 0.2 mole of manganese has been found to be optimum. No advantage is known to be gained by exceeding the limits as presented, since higher proportions of manganese and barium reduce the output of the resultant phosphors to below a usable intensity.

In the application of this invention to actual practice, we find a convenient source of the additive to be barium chloride of ordinary analytical reagent grade. However the barium may also be supplied as the carbonate, oxide, or any other compound that will react with the other components of the phosphor at the temperatures used in the heat treatment of the materials, provided the chloride is supplied by some source such as cadmium chloride. Cadmium is best supplied as the oxide, although other compounds such-as the hydroxide, carbonate and phosphate have been found equally as effective." The phosphate may 7 The raw materials are intimately mixed by blending and grinding or hammer milling, or they may be milled in a wet state,'such as in an acetone suspension. After mixing, and dryin in the event or wet mixing, the powder is placed in a covered tray, or plugged tube, and fired for 1 to 4 hours at 950 C. to 600 C., respectively. For the above p po ns, /2 hours at 800 C. have been found to be convenient. Phosphors prepared according to these directions have displayed a 45 per cent improvement in fluorescence output over cadmium phosphate phosphors without the added barium chloride.

Example 14 Moles Cadmium carbonate 7.00 Di-ammonium acid phosphate 7.50 Barium carbonate (BaC-Oa) 2.00 Hydrated cadmium chloride 2.00 Hydrated manganese chloride 0.20

The'same procedure is used as in Example 13. This example is given as an alternate method of daeriving the same phosphor as that of Example Example 15 Moles Cadmium carbonate l 9.00

Phosphoric acid 7.50

Barium chloride 2.00

Hydrated manganese chloride 0.20

A solution is made of the barium and manganese chlorides. To this is added the cadmium carbonate and phosphoric acid. The mixture is then evaporated to dryness and ground, followed by a heat treatment as previously described. The

= resultant phosphor is the same as that of Ex- 1 phosphate phosphors.

9 -We 'also ''propose to use -combinations -of :any and all of the above modifications. That is, we propose to employ both (1) -and'(2) both'(l)'and (3),- both (2) and (3), orall'of (1), (2)and (3) in phosphors to get improvementsoverthe unmodified cadmium phosphate phosphor.

The sole figure represents the outputs obtainable from combinations of zinc, barium and strontium chlorides in cadmium phosphate phosphor. The triaxial diagram denotes all possible combinations of zinc, barium and strontium chlorides in the formulation:

3Cd3 (PO4),2'2 (Zn, Ba, Sr) C12:0.2MI1

The numerals superimposed onthe chart represent plaque brightness va'ues of thecompositions represented by the 're'riods. For example, a phosphor of composition A, would consist of the following ingredients by mole per cent; 25% Z1'1C12, 25% Bach and 50% SrClz "or by molar proportions would be represented by the formula:

3Cd3 (P04) 2 0.5ZnCl2 0.5BaCl2 1.0SrCl2:0.2Mn

However, the brightnesses of the phosphors are dependent upon the temperaturev of preparation. In variations of zinc, barium and "strontium halides, various ture; for high barium contents are near 700 for high strontium 850 0., and for high zinc phors. Consequently, the selection of a higher firing temperature for the entireseries would result in a displacement of the higher brightness values towards higher strontium containing phosphors since thes would then be subjected to the optimum firingtemperatures, whereas" the compositions containing higher barium would be lower in output because of 'overfiring.

The second consideration concerns themole ratio of total halide to cadmiumphosphate. is mentioned in the disc'osure, the optimum amounts. of -zinc, barium and strontium are .1. 2 andv 2 moles respectively per =3 molesofacadmium phosphate when each is used singly. The greatest of these is'twomoles of the chloride hence the chartof compositions is so chosen that all combinations provide a ratio of 3 moles of cadmium phosphate to 2 moles of total .chlorides. .I-Ioweve'r, it permissible 1 to :choose ;a

ratio of otherithansfi to 2sasis:pnesented inzthe,

chart. Actually, the total halidemay be varied from 205 :to "5:0 moles-per 3-moles of cadmium phosphate. Such a change-would cause a shift in the position of the maximum of point B. Consider, for example,-a decreaseto ,atotalghalide content of 1 mole per 3 molesof cadmiumphos- Thedecrease would then favorthe' optimum amount of zinc chloride, which .is 1.0,mole, and consequently shift the maximum towards the zinc chloride corner of the chart.

Consider, now, a change in the opposite. direction, that is an increasein the totalhalide content to 5 moles of chlorides per 3 moles of cadmium phosphate. Since the increase-tofimoles constitutes a large excess over that-amount which is optimum, thatis a total of 2 moles, then-the situation becomes one where thetolerability-of the excess chlorides becomes important. That is, excess amounts of the three chlorides-ofzino, barium, and strontium aifect the brightness :by variable degrees. The brightness. ismost sensitive to zinc, lesser to strontium, .andileast to barium excesses. Therefore, in mixtures .of :50 moles of total chlorides, higher brightness values would be obtained nearer the bariumcorneraof the chart.

To summarize the foregoing; the position .of the maximum at point B in the figure.-is-..de pendent upon the firing temperature of thephosphors and the ratio of total chlorides to cadmium phosphate. An increase in'firing temperature shifts the maximum towards the strontium corner, a decrease in firingtemperatures'favors the barium corner. A decrease initotal' halide shifts the maximum toward the zinc'corner and an increase in total chloride shifts'the maximum .towards the barium corner.

From the foregoing it willbe'seenthat we have modified manganese activated cadmium phosphate in various ways, coated to optimum densities the phosphors so produced on bulbs, and baked in a lehr temperature range. of 593 TC.'to 621 C. Such conditions yield higher zero and 100 hr. lumens per watt andtmaximum maintenance. The-highest average values obtained were 68.2 and 61.2. lumens, per watt at zero. at 100 hrspand in some instances 93.3% maintenance. Color analysesofthese lamps indicate that the phosphor must be accompanied. by small percentages of blue and green emitting phosphors to make conventional white fluorescent lamps. g

The following are examples of the propertions which may be blended tdpro'ducerapproximately' 3500" white fluorescent lamps:

Example .16

Percent by :iweight Phosphor of Example,1 to {'86 Zinc silicate phosphor ,10i:to 'fl Magnesium tungstate phosphor ,10 .to '7 Example 17 Percent Icy-weight Phosphor of Example 3 -182 to88 Zinc silicate phosphor *Qlto 1J6 Magnesium tungstate phosphor 910 "6 Example 18 Perccntrbywrtight Phosphor of Example 6 79.-to:;'85 Zinc silicate phosphor ;-'9-.:to :36-

Magnesium tungstate phosphorsflmh 1'2rto' 2.9

Example 19 Percent by wei h Phosphor vofiiixan 1pl e ,10 -...7.8 to .85 Zmc silicate phosphor" lito lo 8 to 5 1 Example Percent by weight Phosphor of Example 13 82 to 88 Zinc silicate phosphor 9 to 6 Magnesium tungstate phosphor 9 to 6 Increasing proportions of barium and strontium chlorides, above a certain minimum concentration, increase the output. The additions of various metal halides to a base material of tertiary cadmium phosphate activated by manganese has thus resulted in the formation of halophosphates with magnesium chloride, magnesium fluoride, zinc chloride, zinc fluoride, strontium chloride, and barium chloride, although examples giving only the chloride substitutions have been furnished. However, corresponding fiuorides may in the examples be substituted, mole for mole.

Increasing amounts of strontium chloride with increasing amounts of manganese cause the peak emission to shift a maximum of 120 A. U. toward the red. However, if either manganese or strontium is held to a small amount, an increase in the other will not produce such a shift. The formula for maximum shift is 3Cd3(PO4)2:3SrClz:l.0Mn. Extremely high plaque brightness was obtainable from a formulation of and the emission is peaked at 5880 A. U. AS the red emission has been fortified by the presence of strontium in the phosphor, it is possible to derive spectral distributions from a blend comparable to that obtainable by the use of zinc beryllium silicate. Barium additions result in fluorescent efficiencies equal to those obtainable by zinc and strontium additions. The replacement of cadmium oxide by cadium carbonate has been considered as a means of eliminating an unwanted reaction of the raw materials which caused troublesome caking and complications in mixing. 7 In the claims, the word halogen is to be interpreted as including only chlorine and fluorine, and the word halide is to be interpreted as including only chloride and fluoride.

Although preferred embodiments have been disclosed, it will be understood that modifications may be made within the spirit and scope of the invention.

We claim:

'1. A luminescent composition consisting essentially of the fired reaction product of the following constituents in about the stated proportions: cadmium oxide, 9 moles; ammonium acid phosphate, 7.50 moles; magnesium chloride, 0.6 mole; zinc chloride, 0.4 mole; and manganese chloride, 0.2 mole.

2. A luminescent composition consisting essentially of the fired reaction product of the following constituents in about the stated proportions: cadmium carbonate, 9 moles; ammonium acid phosphate, 7.5 moles; magnesium chloride, 0.6 mole; zinc chloride, 0.4 mole; manganese carbonate, 0.2 mole; and ammonium chloride, 0.4 mole.

3. A luminescent composition consisting essentially of the fired reaction product of the following constituents in about the stated proportions; cadmium oxide, 9 moles; phosphoric acid, 7.5 moles; magnesium chloride, 0.6 mole; zinc chloride 0.4 mole, and manganese chloride,

.2 moles r '4. 'A luminescent composition consistingessentially of the fired reaction product of. the

following constituents in about the stated proportions by weight: hydrated cadmium nitrate, 555.3; di-ammonium acid phosphate, 198.5; hydrated magnesium chloride, 24.4; zinc chloride, 10.9; and hydrated manganese chloride, 7.92.

5. A luminescent composition consisting essentially of the fired reaction product of the following constituents in about the stated proportions; cadmium oxide, 9 moles; di-ammonium acid phosphate, 7.5 moles; strontium chloride, 2.0 to 3.0 moles; and manganese chloride, .001 to 2.0 mole.

6. A luminescent composition consisting essentially of the fired reaction product of the following constituents in about the stated proportions: cadmium carbonate, 7.0 moles; monoammoniumacid phosphate, 7.5 moles; strontium carbonate 2.0 to 3.0 moles, cadmium chloride 2.0 moles; and manganese chloride, .001 to 2.0 moles.

7. A luminescent composition consisting essentially of the fired reaction product of the following constituents in about the stated proportions; cadmium oxide, 9 moles; di-ammonium acid phosphate, 7.5 moles; barium chloride, 2 moles; and manganese chloride, 0.2 mole.

SIA luminescent composition consisting essentially of the fired reaction product of the following constituents in about the stated proportions: cadmium carbonate, 7 moles; di-ammonium acid phosphate, 7.5 moles; barium carbonate, 2 moles; cadmium chloride, 2 moles; and manganese chloride, 0.2 mole.

9. A luminescent composition consisting essentially of the fired reaction product of the fol- Q lowing constituentsin about the stated proportionsz' cadmium carbonate, 9 moles; phosphoric acid, 7.5 moles; barium chloride, 2 moles; and manganese chloride,0.2 mole.

10. The method of manufacturing a fluorescent lamp, comprising applying a luminescent composition consisting of cadmium orthophosphate, a halide formed by one of the group consisting of chlorine and fluorine and at least one of the group consisting of magnesium, zinc, strontium, and barium, and manganese in activator proportions; having the gram molecular formula:

where L stands for a halogen of the group consisting of chlorine and fluorine; v is a number lying in the range between and including .05 and 3; w is a number not higher than 3; a: is a number not higher than 5; y is a number not higher than 3; z is a number lying in the range between and including 0.01 and 2; where v is zero if .r or y is higher than zero; where the proportion of only asmany as two of the zinc, strontium and barium components, may be zero; and where the sum of v, w, :c and y is a number lying in the range between and including .05 and 5, to the interior surface of its envelope and then lehring 7 said envelope at a temperature of from 593 C. to 621 C. g

11. The method of making a luminescent composition which will give a white color, comprising blending from 78% to 88% of a phosphor consisting of cadmium orthophosphate, a halide formed by one of the group-consisting of ch10 rine and fluorine and at least one of the group consisting of magnesium, zinc, strontium, and barium, and manganese in activator proportions; having the'gramlnrolecular gamma: 9

13 Where L stands for a halogen of the group consisting of chlorine and fluorine; o is a number lying in the range between and including .05 and 3; w is a number not higher than 3; .1: is a number not higher than 5; y is a number not higher than 3; z is a number lying in the range between and including 0.01 and 2; where o is zero if 1: or y is higher than zero; where the proportion of only as many as two of the zinc, strontium and barium components, may be zero; and where the sum of v, w, a: and y is a number lying in the range between and including .05 and 5, with from 14% to 6% of zinc silicate and from 12% to 5% of magnesium tungstate.

12. A luminescent composition consisting of cadmium orthophosphate, a halide formed by one of the group consisting of chlorine and fluorine and at least one of the group consisting of magnesium, zinc, strontium, and barium, and manganese in activator proportions; having the gram molecular formula:

30d: (P04) 2 'DMgLz wZnLz :rSrLz yBaLz :zMn

where L stands for a halogen of the group consisting of chlorine and fluorine; v is a number lying in the range between and including .05 and 3; w is a number lying in the range not higher than 3; :c is a number lying in the range not higher than 5; y is a number lying in the range not higher than 3; 2 is a number lying in the range between and including 0.01 and 2; where c is zero if x or y is higher than zero; where the proportion of only as many as two of the zinc, strontium and barium components, may be zero; and where the sum of v, w, a: and y is a number lying in the range between and including .05 and 5. 13. The method of making a phosphor of the cadmium phosphate type with a high output, comprising intimately mixing about 231.1 grams of cadmium oxide, 198 grams of di-ammonium acid phosphate, 10.9 grams of zinc chloride, 24.4 grams of hydrated magnesium chloride, 7.92 grams of hydrated manganese chloride, until the preliminary dry state reaction is complete, grinding for at least one hour, and finally firing in a covered tray for 1 to 4 hours at a temperature of 700 C. to 980 0., the shorter time for the higher temperature.

ROBERT W. WOLLENTIN. RUDOLPH NAGY.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,191,351 McKeag Feb. 20, 1940 2,488,733 McKeag Nov. 22, 1949 2,605,227 Fonda July 29, 1952 

12. A LUMINESCENT COMPOSITION CONSISTING OF CADMIUM ORTHOPHOSPHATE, A HALIDE FORMED BY ONE OF THE GROUP CONSISTING OF CHLORINE AND FLUORINE AND AT LEAST ONE OF THE GROUP CONSISTING OF MAGNESIUM, ZINC, STRONTIUM, AND BARIUYM, AND MANGANESE IN ACTIVATOR PROPORTIONS; HAVING THE GRAM MOLECULAR FORMULA; 